1. Field of the Invention
The present invention relates to an emulsion for a photothermographic material, a production process for the photothermographic material and a recording process therefor.
2. Background of the Invention
Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
In thermography three approaches are known:
1. Direct thermal formation of a visible image pattern by imagewise heating of a recording material containing matter that by chemical or physical process changes colour or optical density.
2. Imagewise transfer of an ingredient necessary for the chemical or physical process bringing about changes in colour or optical density to a receptor element.
3. Thermal dye transfer printing wherein a visible image pattern is formed by transfer of a coloured species from an imagewise heated donor element onto a receptor element.
Thermographic materials of type 1 become photothermographic when a photosensitive agent is present which after exposure to UV, visible or IR light is capable of catalyzing or participating in a thermographic process bringing about changes in colour or optical density.
Examples of photothermographic materials are the so called xe2x80x9cDry Silverxe2x80x9d photographic materials of the 3M Company, which are reviewed by D. A. Morgan in xe2x80x9cHandbook of Imaging Sciencexe2x80x9d, edited by A. R. Diamond, page 43, published by Marcel Dekker in 1991.
GB 1 342 525 discloses a photosensitive heat-processable material comprising a support and contained in a layer or layers thereof: (a) an oxidation/reduction image-forming system comprising: (b) a light-insensitive reducible metal compound and (c) an organic reducing agent therefor, (d) a photosensitive silver compound capable, on exposure to actinic radiation, of forming centres which catalyze the thermally induced oxidation/reduction reaction of (b) with (c) to form a visible image, and (e) a substantially colourless photographic speed-increasing onium halide. From the general formulae given in claim 4 of GB-P 1 342 525, the examples of speed-increasing onium halides given in the specification and the onium halides used in the invention examples thereof show that the term halide in this patent is that given in the xe2x80x9cMcGraw-Hill Dictionary of Scientific and Technical Termsxe2x80x9d, Ed. S. P. Parker, McGraw-Hill Book Company, New York (1989) i.e. xe2x80x9ca compound of the type MX, where X is fluorine, chlorine, bromine or astatine, and M is another element or organic radicalxe2x80x9d. Onium halides are, however, not able to stabilize fully photothermographic materials against fogging.
U.S. Pat. No. 3,957,517 discloses a dry method for the stabization of a print-out silver halide photographic material wherein the silver halide is the image-forming substance, which comprises (1) imagewise exposure of a silver halide photographic emulsion material to form a print-out image, wherein said silver halide photographic emulsion material consists essentially of silver halide grains at least 50 mol % of which consists of silver bromide and 0.1 to 33 mol %, based on the silver halide, of an onium compound having an iodide ion or an anion containing iodine, said onium compound being a member selected from the group consisting of compounds of the formulae: 
wherein A is N, P, As or Sb, B is O, S, SO, Se or Sn, and each of R1 to R9 is an alkyl group having less than 8 carbon atoms, or an aryl group having less than 16 carbon atoms, or of said R1 to R9 two groups can be connected to each other to form a ring selected from the group consisting of a pyridine ring, a morpholine ring, an oxazine ring, a thiazine ring, a thiazole ring, an oxazole ring, a benzothiazole ring and a benzo-oxazole ring, and wherein X is an iodine ion or an iodine containing anion; and subsequently heating said photographic material to a temperature of at least 80xc2x0 C., thereby stabilizing said print-out image.
In U.S. Pat. No. 4,173,482 a dry image forming material is disclosed capable of forming an image by preliminary heating, imagewise exposure to light, and heat development thereof, said material comprising (a) a non-photosensitive organic silver salt oxidizing agent, (b) a reducing agent for a silver ion and (c) at least one halogen molecule selected from the group consisting of a bromine molecule, an iodine molecule, iodine chlorides, iodine bromide and bromine chloride and optionally further comprising at least one halogen ion source in addition to said at least one halogen molecule. According to U.S. Pat. No. 4,173,482 (column 3, lines 64-68) the halogen ion source and the halogen molecule may be added separately, or a compound or compounds capable of forming a halogen ion source and a halogen molecule by reaction at the preparation of the image forming material may be used, for example triphenylphosphite nonaiodide. The use of single compound, acting as a halogen ion source and providing a halogen molecule requires the use of an additional preliminary heating step prior to image-wise exposure to actinic light and also partially converts in-situ the non-photosensitive organic silver salt oxidizing agent present into silver halide which is undesirable as regards control over the gradation of the image as expressed by the dependence of optical density upon exposure to actinic light.
U.S. Pat. No. 5,028,523 discloses a photothermographic emulsion comprising silver halide, light-insensitive silver oxidizing compound, reducing agent for silver ion, and a binder, said emulsion also comprising a hydrobromic salt of a nitrogen-containing heterocyclic ring compound associated with a pair of bromine atoms. However, the hydrobromic salt of a nitrogen-containing heterocyclic ring compound associated with a pair of bromine atoms used in the invention example of U.S. Pat. No. 5,028,523, pyridinium hydrobromide perbromide, exhibits a high reactivity with silver behenate to form photosensitive silver bromide which, as is mentioned above, is undesirable as regards control over the gradation of the image as expressed by the dependence of optical density upon exposure to actinic light.
It is therefore a first object of the invention to provide a photothermographic material exhibiting a low fog level upon image-wise exposure and thermal development.
It is therefore a second object of the invention to provide a photothermographic material with low fog level and improved image-gradation, upon image-wise exposure and thermal development.
It is therefore further object of the invention to provide a photothermographic recording process utilizing a photothermographic material not necessitating preliminary heating before image-wise exposure.
Further objects and advantages of the invention will become apparent from the description hereinafter.
According to the present invention, an emulsion is provided comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt and a binder, wherein the emulsion further comprises a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description, or a product of a reaction between the polyhalide compound and a reducing species present in the emulsion.
According to the present invention a process is provided for producing a photothermographic recording material, capable of image formation without preliminary heating prior to exposure, comprising the step of producing a photo-addressable thermally developable element by coating an emulsion, as referred to above, on a support thereby forming an emulsion layer.
According to the present invention, a photothermographic recording material is also provided, capable of image formation without preliminary heating prior to exposure, comprising a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt, an organic reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a binder, wherein the photo-addressable thermally developable element further comprises a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test specified in the description.
According to the present invention, a photothermographic recording process is also provided comprising the steps of: (i) image-wise exposing a photothermographic recording material, as referred to above, to a source of actinic radiation; and (ii) thermally developing the image-wise exposed photothermographic recording material.
Preferred embodiments of the invention are disclosed in the dependent claims.
According to the present invention, an emulsion is provided comprising a polyhalide compound selected from the group consisting of quaternary ammonium polyhalides, quaternary phosphonium polyhalides and ternary sulphonium polyhalides, which satisfies a test given below, or a product of a reaction between the polyhalide compound and a reducing species present in the emulsion.
The test which the polyhalide compounds used according to the present invention must satisfy is carried out as follows:
i) disperse silver behenate in deionized water by rapidly mixing with the anionic sulfonate dispersion agents, such as Ultravon(trademark) W and Mersolat(trademark) H80 paste, with quantities of water and dispersion agents to produce a predispersion containing 20% by weight of silver behenate and then homogenize with a microfluidizer to a finely divided and stable dispersion. Adjust the pH of the resulting dispersion to about 6.5;
ii) Add the following ingredients with stirring to 1.5 g of the silver behenate dispersion: 1 g of a 30% by weight concentration of a latex-copolymer, such as that obtained by copolymerizing methyl methacrylate, butadiene and itaconic acid in a weight ratio of 45:45:10, 0.013 g of succinimide, 0.1 g of a 11% by weight solution of saponin in a mixture of deionized water and methanol and an aqueous solution of a halogen compound capable of converting silver behenate into silver halide in a quantity corresponding to a concentration of 8 mol % with respect to the silver behenate present;
iii) Doctor-blade a subbed polyethylene terephthalate support having a thickness of 100 xcexcm with the silver behenate/silver bromide dispersion at a blade setting of 60 xcexcm. Dry for several minutes at 40xc2x0 C. on the coating bed and then doctor blade the emulsion layer with a 2.44% by weight aqueous solution of the reducing agent 3-(3,4-dihydroxyphenyl)propionic acid at a blade setting of 30 xcexcm. Allow the resulting thermographic material to dry on the coating bed for several minutes at 40xc2x0 C. and then dry for 1 hour in a hot air oven at 50xc2x0 C.;
iv) Expose the thermographic material to ultra-violet light in an Agfa-Gevaert(trademark) DL 2000 exposure apparatus and then heat on a heated metal block for 10 s at 95xc2x0 C.
In order to satisfy this test the optical density of the exposed and thermally developed material as measured with a densitometer, such as a MacBethm(trademark) TR924 densitometer with a visible filter, must be less than 0.3.
An optical density of less than 0.3 indicates that little photosensitive silver halide is formed due to reaction between the compound being evaluated and silver behenate. However, the hydrobromic salts of nitrogen-containing heterocyclic ring compounds associated with a pair of bromine atoms, as disclosed in U.S. Pat. No. 5,028,523, did not satisfy this test, optical densitiesxe2x89xa71.2 being observed, which indicates the formation of a considerable quantity of photosensitive silver halide due to reaction between such compounds and silver behenate.
In a preferred embodiment of the present invention, the polyhalide compound is selected from the group of polyhalide compounds consisting of tetramethylammonium chloride perbromide, trimethylphenylammonium bromide perbromide and tetramethylammonium-bromide perbromide.
The quaternary ammonium, quaternary phosphonium and ternary sulphonium polyhalides, used according to the present invention, may be added as solids or solutions or may be formed in the dispersion of particles of the substantially light-insensitive silver salt by metathesis between a salt with polyhalide anions and onium salts with anions other than polyhalide.
Preferred polyhalide anions, used according to the present invention, consist of chlorine, bromine and iodine atoms.
The quaternary ammonium, quaternary phosphonium and ternary sulphonium polyhalides, used according to the present invention, may be polymeric or non-polymeric.
Suitable non-polymeric onium salts for use according to the present invention are the quaternary ammonium polyhalides (QAP""s):
QAP01=tetramethylammonium chloride perbromide
QAP02=trimethylphenylammonium bromide perbromide
QAP03=tetramethylammonium bromide perbromide
The quaternary ammonium, quaternary phosphonium and ternary sulphonium polyhalides, used according to the present invention, are preferably present in quantities of between 0.1 and 5.0 mol % with respect to the quantity of substantially light-insensitive organic silver salt of organic, with quantities between 0.4 and 2.4 mol % being particularly preferred.
The photo-addressable thermally developable element, according to the present invention, comprises a substantially light-insensitive silver salt of a fatty acid, photosensitive silver halide in catalytic association therewith and an organic reducing agent in thermal working relationship with the substantially light-insensitive silver salt of a fatty acid and a binder. The element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt ingredients, spectral sensitizer optionally together with a supersensitizer in intimate sensitizing association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilization of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent, if present, are in thermal working relationship with the substantially light-insensitive organic silver salt i.e. during the thermal development process the reducing agent and the toning agent, if present, are able to diffuse to the substantially light-insensitive silver salt of a fatty acid.
Preferred substantially light-insensitive organic silver salts used according to the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called xe2x80x9csilver soapsxe2x80x9d; silver dodecyl sulphonate described in U.S. Pat. No. 4,504,575; and silver di-(2-ethylhexyl)sulfosuccinate described in EP-A 227 141. Modified aliphatic carboxylic acids with thioether group as described e.g. in GB-P 1,111,492 and other organic silver salts as described in GB-P 1,439,478, e.g. silver benzoate and silver phthalazinone, may be used likewise to produce a thermally developable silver image. Further are mentioned silver imidazolates and the substantially light-insensitive inorganic or organic silver salt complexes described in U.S. Pat. No. 4,260,677.
The photosensitive silver halide used in the present invention may be employed in a range of 0.75 to 25 mol percent and, preferably, from 2 to 20 mol percent of substantially light-insensitive organic silver salt.
The silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide etc. The silver halide may be in any form which is photosensitive including, but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonal etc. and may have epitaxial growth of crystals thereon.
The silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc., a reducing agent such as a tin halide etc., or a combination thereof. The details of these procedures are described in T. H. James, xe2x80x9cThe Theory of the Photographic Processxe2x80x9d, Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter 5, pages 149 to 169.
A suspension of particles containing a substantially light-insensitive organic silver salt may be obtained by using a process, comprising simultaneous metered addition of a solution or suspension of an organic compound with at least one ionizable hydrogen atom or its salt; and a solution of a silver salt to a liquid, as described in EP-A 754 969.
The silver halide may be added to the photo-addressable thermally developable element in any fashion which places it in catalytic proximity to the substantially light-insensitive organic silver salt. Silver halide and the substantially light-insensitive organic silver salt which are separately formed, i.e. ex-situ or xe2x80x9cpreformedxe2x80x9d, in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them for a long period of time. Furthermore, it is effective to use a process which comprises adding a halogen-containing compound to the organic silver salt to partially convert the substantially light-insensitive organic silver salt to silver halide as disclosed in U.S. Pat. No. 3,457,075.
A particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide, used according to the present invention is that disclosed in U.S. Pat. No. 3,839,049, but other methods such as those described in Research Disclosure, June 1978, item 17029 and U.S. Pat. No. 3,700,458 may also be used for producing the emulsion.
In a preferred embodiment of the present invention, the emulsion further comprises a reducing agent for silver ion.
Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts in photo-addressable thermally developable coated from non-aqueous media are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, mono-, bis-, tris- or tetrakis-phenols; mono- or bis-naphthols; di- or polyhydroxy-naphtalenes; di- or polyhydroxybenzenes; hydroxymonoethers such as alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in U.S. Pat. No. 3,094,41; pyrazolidin-3-one type reducing agents, e.g. PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; 3-pyrazolines; pyrazolones; reducing saccharides; aminophenols e.g. METOL (tradename); p-phenylenediamines, hydroxylamine derivatives such as for example described in U.S. Pat. No. 4,082,901; reductones e.g. ascorbic acids; hydroxamic acids; hydrazine derivatives; amidoximes; n-hydroxyureas; and the like, see also U.S. Pat. Nos. 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
Polyphenols such as the bisphenols used in the 3M Dry Silver(trademark) materials, sulfonamide phenols such as used in the Kodak Dacomatic(trademark) materials, and naphthols are particularly preferred for photothermographic recording materials with photo-addressable thermally developable elements on the basis of photosensitive silver halide/organic silver salt/reducing agent.
Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts in photo-addressable thermally developable coated from aqueous media are organic compounds containing at least one active hydrogen atom linked to O, N or C. Particularly suitable organic reducing agents for the reduction of the substantially light-insensitive organic silver salt in such photo-addressable thermally developable elements are non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compounds with at least three substituents one of which is a hydroxy group at a first carbon atom and a second of which is a hydroxy or amino-group substituted on a second carbon atom one, three or five ring atoms removed in a system of conjugated double bonds from the first carbon atom in the compound, in which (i) the third substituent may be part of an annelated carbocyclic or heterocyclic ring system; (ii) the third substituent or a further substituent is not an aryl- or oxo-aryl-group whose aryl group is substituted with hydroxy-, thiol- or amino-groups; and (iii) the third substituent or a further substituent is a non-sulfo-electron withdrawing group if the second substiuent is an amino-group.
In preferred reducing agents, the ring atoms of the non-sulfo-substitued 6-membered aromatic or heteroaromatic ring compound consist of nitrogen and carbon ring atoms and the non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compound is annelated with an aromatic or heteroaromatic ring system.
In further preferred reducing agents, the non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compound is substituted with one or more of the following substituents which may also be substituted: alkyl, alkoxy, carboxy, carboxy ester, thioether, alkyl carboxy, alkyl carboxy ester, aryl, sulfonyl alkyl, sulfonyl aryl, formyl, oxo-alkyl and oxo-aryl.
Particularly preferred reducing agents are substituted catechols or substitued hydroquinones with 3-(3xe2x80x2,4xe2x80x2-dihydroxyphenyl)-propionic acid, 3xe2x80x2,4xe2x80x2-dihydroxy-butyrophenone, methyl gallate, ethyl gallate and 1,5-dihydroxy-naphthalene being especially preferred.
During the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the substantially light-insensitive organic silver salt particles so that reduction of the substantially light-insensitive organic silver salt can take place.
During the thermal development process the reducing agent must be present in such a way that it is able to diffuse to said substantially light-insensitive organic heavy metal salt particles so that reduction of said organic heavy metal salt can take place.
The silver image density depends on the coverage of the above defined reducing agent(s) and organic silver salt(s) and has to be preferably such that, on heating above 80xc2x0 C., an optical density of at least 2.5 can be obtained. Preferably at least 0.10 moles of reducing agent per mole of organic heavy metal salt is used.
The above mentioned reducing agents, regarded as primary or main reducing agents, may be used in conjunction with so-called auxiliary reducing agents. Auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are sulfonyl hydrazide reducing agents such as disclosed in U.S. Pat. No. 5,464,738, trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in U.S. Pat. No. 5,496,695 and organic reducing metal salts, e.g. stannous stearate described in U.S. Pat. Nos. 3,460,946 and 3,547,648.
The photo-addressable thermally developable element of the photothermographic recording material, used according to the present invention, may contain a spectral sensitizer, optionally together with a supersensitizer, for the silver halide. The silver halide may be spectrally sensitized with various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes optionally, particularly in the case of sensitization to infra-red radiation, in the presence of a so-called supersensitizer. Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus. In the above described cyanine and merocyanine dyes, those having imino groups or carboxyl groups are particularly effective. Suitable sensitizers of silver halide to infra-red radiation include those disclosed in the EP-A""s 465 078, 559 101, 616 014 and 635 756, the JN""s 03-080251, 03-163440, 05-019432, 05-072662 and 06-003763 and the U.S. Pat. Nos. 4,515,888, 4,639,414, 4,713,316, 5,258,282 and 5,441,866. Suitable supersensitizers for use with infra-red spectral sensitizers are disclosed in EP-A""s 559 228 and 587 338 and in the U.S. Pat. Nos. 3,877,943 and 4,873,184.
The film-forming binder for the photo-addressable thermally developable element used according to the present invention may be coatable from a solvent or aqueous dispersion medium.
The film-forming binder for the photo-addressable thermally developable element used according to the present invention may be coatable from a solvent dispersion medium, used according to the present invention, may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g. polymers derived from xcex1,xcex2-ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
The film-forming binder for the photo-addressable thermally developable element coatable from an aqueous dispersion medium, used according to the present invention, may be all kinds of transparent or translucent water-dispersible or water soluble natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously for example proteins, such as gelatin and gelatin derivatives (e.g. phthaloyl gelatin), cellulose derivatives, such as carboxymethylcellulose, polysaccharides, such as dextran, starch ethers etc., galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, homo- or co-polymerized acrylic or methacrylic acid, latexes of water dispersible polymers, with or without hydrophilic groups, or mixtures thereof. Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described e.g. in U.S. Pat. No. 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
The binder to organic heavy metal salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the photo-addressable thermally developable element is preferably in the range of 5 to 50 xcexcm.
The above mentioned binders or mixtures thereof may be used in conjunction with waxes or xe2x80x9cheat solventsxe2x80x9d also called xe2x80x9cthermal solventsxe2x80x9d or xe2x80x9cthermosolventsxe2x80x9d improving the reaction speed of the redox-reaction at elevated temperature.
By the term xe2x80x9cheat solventxe2x80x9d in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50xc2x0 C. but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic heavy metal salt, at a temperature above 60xc2x0 C.
In order to obtain a neutral black image tone in the higher densities and neutral grey in the lower densities the recording layer contains preferably in admixture with said organic heavy metal salts and reducing agents a so-called toning agent known from thermography or photo-thermography.
Suitable toning agents are succinimide and the phthalimides and phthalazinones within the scope of the general formulae described in U.S. Pat. No. 4,082,901. Further reference is made to the toning agents described in U.S. Pat. Nos. 3,074,809, 3,446,648 and 3,844,797. Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type as described in GB-P 1,439,478, U.S. Pat. Nos. 3,951,660 and 5,599,647.
Antihalation Dyes
In addition to said ingredients, the photothermographic recording material of the present invention may contain antihalation or acutance dyes which absorb light which has passed through the photosensitive layer, thereby preventing its reflection. Such dyes may be incorporated into the photo-addressable thermally developable element or in any other layer comprising the photothermographic recording material of the present invention. The antihalation dye may also be bleached either thermally during the thermal development process, as disclosed in the U.S. Pat. Nos. 4,033,948, 4,088,497, 4,153,463, 4,196,002, 4,201,590, 4,271,263, 4,283,487, 4,308,379, 4,316,984, 4,336,323, 4,373,020, 4,548,896, 4,594,312, 4,977,070, 5,258,274, 5,314,795 and 5,312,721, or photo-bleached after removable after the thermal development process, as disclosed in the U.S. Pat. Nos. 3,984,248, 3,988,154, 3,988,156, 4,111,699 and 4,359,524. Furthermore the antihalation layer may be contained in a layer which can be removed subsequent to the exposure process, as disclosed in U.S. Pat. No. 4,477,562 and EP-A 491 457. Suitable antihalation dyes for use with infra-red light are described in the EP-A""s 377 961 and 652 473, the EP-B""s 101 646 and 102 781 and the U.S. Pat. Nos. 4,581,325 and 5,380,635.
In order to obtain improved shelf-life and reduced fogging, stabilizers and antifoggants may be incorporated into the thermographic and photothermographic materials of the present invention. Examples of suitable stabilizers and antifoggants and their precursors, which can be used alone or in combination, include the thiazolium salts described in U.S. Pat. Nos. 2,131,038 and 2,694,716; the azaindenes described in U.S. Pat. Nos. 2,886,437 and 2,444,605; the urazoles described in U.S. Pat. No. 3,287,135; the sulfocatechols described in U.S. Pat. No. 3,235,652; the oximes described in GB-P 623,448; the thiuronium salts described in U.S. Pat No. 3,220,839; the palladium, platinum and gold salts described in U.S. Pat. Nos. 2,566,263 and 2,597,915; the tetrazolyl-thio-compounds described in U.S. Pat. No. 3,700,457; the mesoionic 1,2,4-trizazolium-3-thiolate stablizer precursors described in U.S. Pat. Nos. 4,404,390 and 4,351,896; the tribromomethyl ketone compounds described in EP-A 600 587; the combination of isocyanate and halogenated compounds described in EP-A 600 586; the vinyl sulfone and xcex2-halo sulfone compounds described in EP-A 600 589; and those compounds mentioned in this context in Chapter 9 of xe2x80x9cImaging Processes and Materials, Neblette""s 8th editionxe2x80x9d, by D. Kloosterboer, edited by J. Sturge, V. Walworth and A. Shepp, page 279, Van Nostrand (1989); in Research Disclosure 17029 published in June 1978; and in the references cited in all these documents.
In addition to said ingredients the photo-addressable thermally developable element may contain other additives such as free fatty. acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F3C(CF2)6CONH(CH2CH2O)xe2x80x94H, silicone oil, e.g. BAYSILONE xc3x96l A (tradename of BAYER AG-GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, colloidal silica, fine polymeric particles [e.g. of poly(methylmethacrylate)] and/or optical brightening agents.
The support for the photothermographic recording material used according to the present invention may be transparent, translucent or opaque, e.g. having a white light reflecting aspect and is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate as disclosed in GB 1,293,676, GB 1,441,304 and GB 1,454,956. For example, a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and said paper base substrate.
The support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive recording layer. The support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP""s 194 106 and 234 563 and U.S. Pat. Nos. 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, said base may be colourless or coloured, e.g. having a blue colour.
One or more backing layers may be provided to control physical properties such as curl or static.
According to a preferred embodiment of the photothermographic recording material of the present invention, the photo-addressable thermally developable element is provided with a protective layer to avoid local deformation of the photo-addressable thermally developable element, to improve its resistance against abrasion and to prevent its direct contact with components of the apparatus used for thermal development.
This protective layer may have the same composition as an anti-sticking coating or slipping layer which is applied in thermal dye transfer materials at the rear side of the dye donor material or protective layers used in materials for direct thermal recording.
The protective layer preferably comprises a binder, which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible. Among the hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred. Suitable hydrophilic binders are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred and polyvinylalcohol being particularly preferred.
A protective layer used according to the present invention may be crosslinked. Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
A protective layer used according to the present invention may comprise in addition at least one solid lubricant having a melting point below 150xc2x0 C. and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative, further dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer. Examples of suitable lubricating materials are surface active agents, liquid lubricants, solid lubricants which do not melt during thermal development of the recording material, solid lubricants which melt (thermomeltable) during thermal development of the recording material or mixtures thereof. The lubricant may be applied with or without a polymeric binder.
Such protective layers may also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198. Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
In a preferred embodiment the recording material of the present invention an antistatic layer is applied to the outermost layer not comprising at least one solid lubricant having a melting point below 150xc2x0 C. and at least one liquid lubricant in a binder, wherein at least one of said lubricants is a phosphoric acid derivative. Suitable antistatic layers therefor are described in EP-A""s 444 326, 534 006 and 644 456, U.S. Pat. Nos. 5,364,752 and 5,472,832 and DOS 4125758.
In a preferred embodiment of the present invention, the emulsion layer is overcoated with a layer comprising a polymer and said emulsion layer and/or said overcoat layer further comprise(s) an organic reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt.
The coating of any layer of the recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, N.Y. 10010, U.S.A.
Photothermographic materials, used according to the present invention, may be exposed with radiation of wavelength between an X-ray wavelength and a 5 microns wavelength with the image either being obtained by pixel-wise exposure with a finely focussed light source, such as a CRT light source; a UV, visible or IR wavelength laser, such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780 nm, 830 nm or 850 nm; or a light emitting diode, for example one emitting at 659 nm; or by direct exposure to the object itself or an image therefrom with appropriate illumination e.g. with UV, visible or IR light.
For the thermal development of image-wise exposed photothermo-graphic recording materials, used according to the present invention, any sort of heat source can be used that enables the recording materials to be uniformly heated to the development temperature in a time acceptable for the application concerned e.g. contact heating, radiative heating, microwave heating etc.
A photothermographic recording process is further provided, according to the present invention, wherein subsequent to imagewise exposure no further heating is required to stabilize the image.
The photothermographic recording materials of the present invention can be used for both the production of transparencies and reflection type prints. This means that the support will be transparent or opaque, e.g. having a white light reflecting aspect. For example, a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and said paper base substrate. Should a transparent base be used, said base may be colourless or coloured, e.g. has a blue colour.
In the hard copy field photothermographic recording materials on a white opaque base are used, whereas in the medical diagnostic field black-imaged transparencies are widely used in inspection techniques operating with a light box.
While the present invention will hereinafter be described in connection with a preferred embodiment thereof, it will be understood that it is not intended to limit the invention to that embodiment. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included in the spirit and scope of the invention as defined by the appending claims.
The following ingredients in addition to those mentioned above were used in the photothermographic recording materials of the invention examples and comparative examples illustrating the present invention in the antistatic layer:
KELZAN(trademark) S: a xanthan gum from MERCK and CO., Kelco Division, USA, which according to Technical Bulletin DB-19 is a polysaccharide containing mannose, glucose and glucuronic repeating units as a mixed potassium, sodium and calcium salt;
PT-dispersion: a dispersion of poly(3,4-ethylenedioxy-thiophene)/ploystyrene sulphonic acid produced by. the polymerization of 3,4-ethylenedioxy-thiophene in the presence of polystyrene sulphonic acid and ferric sulphate as described in U.S. Pat. No. 5,354,613;
ULTRAVON(trademark) W: an aryl sulfonate from CIBA-GEIGY;
PERAPRET(trademark) PE40: a 40% aqueous dispersion of polyethylene wax from BASF;
KIESELSOL(trademark) 100F: a 36% aqueous dispersion of colloidal silica from BAYER;
MAT01: 20% aqueous dispersion of particles of methyl-methacrylate(98% by weight)-stearylmethacrylate(2% by weight)-copolymeric beads with an average particle size of 5.9 xcexcm produced as described in U.S. Pat No. 4,861,812;
LATEX01: a 12% by weight dispersion of polymethyl methacrylate with an average particle size of 88.8 nm prepared as described in U.S. Pat. No. 5,354,613;
D01:
in the photo-addressable thermally developable element:
GEL: phthaloylgelatin, type 16875 from ROUSSELOT;
PHP: pyridinium hydrobromide perbromide;
Butvar(trademark) B76: polyvinylbutyral from MONSANTO;
SENSI: 
LOWINOX(trademark) 22IB46: 2-propyl-bis(2-hydroxy-3,5-dimethylphenyl)methane from CHEM. WERKE LOWI;
TMPS: tribromomethyl benzenesulfinate;
and in the protective layer:
CAB: cellulose acetate butyrate, CAB-171-15S from EASTMAN;
PMMA: polymethylmethacrylate, Acryloid(trademark) K120N from ROHM and HAAS;
LOWINOX(trademark) 22IB46: 2-propyl-bis(2-hydroxy-3,5-dimethylphenyl)methane from CHEM. WERKE LOWI.